Effect of Zinc Humate on Growth of Soybean and Wheat in Zinc‐Deficient Calcareous Soil

Abstract

Humic acids have many benefits for plant growth and development, and these effects may be maximized if these materials are combined with micronutrient applications. In the present study, pot experiments were conducted to evaluate the effects of zinc (Zn) humate and ZnSO₄ on growth of wheat and soybean in a severely Zn‐deficient calcareous soil (DTPA‐Zn: 0.10 mg kg^?1 soil). Plants were grown for 24 (wheat) and 28 days (soybean) with 0 or 5 mg kg^?1 of Zn as either ZnSO₄ or Zn humate. Zinc humate used in the experiments was obtained from Humintech GmbH, Germany, and contained 5% of Zn. When Zn was not supplied, plants rapidly developed visible symptoms of Zn deficiency (e.g., chlorosis and brown patches on young leaves in soybean and necrotic patches on middle‐aged leaves in wheat). Adding Zn humate eliminated Zn‐deficiency symptoms and enhanced dry matter production by 50% in soybean and 120% in wheat. Zinc‐humate and ZnSO₄ were similarly effective in increasing dry matter production in wheat; but Zn humate increased soybean dry matter more than ZnSO₄. When Zn was not supplied, Zn concentrations were 6 mg kg^?1 for wheat and 8 mg kg^?1 for soybean. Application of Zn humate and ZnSO₄ increased shoot Zn concentration of plants to 36 and 34 mg kg^?1 in wheat and to 13 and 18 mg kg^?1 in soybean, respectively. The results indicate that soybean and wheat plants can efficiently utilize Zn chelated to humic acid in calcareous soils, and this utilization is comparable to the utilization of Zn from ZnSO₄. Under Zn‐deficient soil conditions, plant growth and yield can be maximized by the combined positive effects of Zn and humic acids.     

Transformation and Availability of Various Forms of Zinc in Soils

The transformation and availability of various forms of Zn applied into a cinnamon soil and a carbonate meadow soil as well as the effects of fertillizer-P on them were studied by using the field experiment method and chemically sequential extraction procedure.Zn added into the soils was found to be rapidly transformed into the various forms. In the cinnamon soil,the amount of Zn transformed into the carbonate bound form was the highest,and the carbonate bound form was proven by the analyses of intensity factor and capacity factor to be the primary available Zn pool.But in the carbonate meadow soil,the Zn transformed was relatively homogeneously distributed in the various forms though the amount of Zn transformed into the Mn-oxide bound form was relatively high,and the organically bound,Mn-oxide bound and amorphous Fe-oxide,bound forms were found to be the main available Zn pool.Fertilizer-P took part in the regulation and control of available Zn in the soils to a certain degree.In the carbonate meadow soil,application of P fertilizer probably aggravated Zn deficiency at low Zn rate,while it was favorable to the storage of available Zn in the case of high Zn rate.     

Influence of Gyttja on Shoot Growth and Shoot Concentrations of Zinc and Boron of Wheat Cultivars Grown on Zinc‐Deficient and Boron‐Toxic Soil

Abstract

Greenhouse experiments were carried out to study the influence of gyttja, a sedimentary peat, on the shoot dry weight and shoot concentrations of zinc (Zn) and boron (B) in one bread wheat (Triticum aestivum L., cv. Bezostaja) and one durum wheat (Triticum durum L., cv. Kiziltan) cultivar. Plants were grown in a Zn‐deficient (DTPA‐Zn: 0.09 mg kg^?1 soil) and B‐toxic soil (CaCl₂/mannitol‐extractable B: 10.5 mg kg^?1 soil) with (+Zn = 5 mg Zn kg^?1 soil) and without (?Zn = 0) Zn supply for 55 days. Gyttja containing 545 g kg^?1 organic matter was applied to the soil at the rates of 0, 1, 2.5, 5, and 10% (w/w). When Zn and gyttja were not added, plants showed leaf symptoms of Zn deficiency and B toxicity, and had a reduced growth. With increased rates of gyttja application, shoot growth of both cultivars was significantly enhanced under Zn deficiency, but not at sufficient supply of Zn. The adverse effects of Zn deficiency and B toxicity on shoot dry matter production became very minimal at the highest rate of gyttja application. Increases in gyttja application significantly enhanced shoot concentrations of Zn in plants grown without addition of inorganic Zn. In Zn‐sufficient plants, the gyttja application up to 5% (w/w) did not affect Zn concentration in shoots, but at the highest rate of gyttja application there was a clear decrease in shoot Zn concentration. Irrespective of Zn supply, the gyttja application strongly decreased shoot concentration of B in plants, particularly in durum wheat. For example, in Zn‐deficient Kiziltan shoot concentration of B was reduced from 385 mg kg^?1 to 214 mg kg^?1 with an increased gyttja application. The results obtained indicate that gyttja is a useful organic material improving Zn nutrition of plants in Zn‐deficient soils and alleviating adverse effects of B toxicity on plant growth. The beneficial effects of gyttja on plant growth in the Zn‐deficient and B‐toxic soil were discussed in terms of increases in plant available concentration of Zn in soil and reduction of B uptake due to formation of tightly bound complexes of B with gyttja.     

Relative Efficiency of Zinc Sulfate and Zinc Oxide–Coated Urea in Rice–Wheat Cropping System

Abstract

Rice–wheat cropping system covers about 24 million hectares in China, India, Pakistan, Nepal, and Bangladesh, and zinc deficiency is widespread in rice–wheat belts of all these five countries. The current practice of applying zinc sulfate heptahydrate (ZnSO₄ · 7H₂O) to soil is problematic because of the poor quality of the nutrients available in the market to the farmers. Zinc (Zn)–coated urea is therefore being manufactured to guarantee a good‐quality Zn source. This article reports the results from a field study conducted to study the relative efficiency of zinc sulfate and zinc oxide (ZnO)–coated ureas in rice–wheat cropping system. The highest grain yield of rice–wheat cropping system was obtained with 2.0% coating of urea. Zinc sulfate was also a better coating material than ZnO. Partial factor productivity, agronomic efficiency, apparent recovery, and physiological efficiency of applied Zn decreased as the level of Zn coating was increased.     

Fractionation of Zinc in Paddy Soils of China

The rice fields in China amount to 25.4 million hectares of which low yield paddy soils areabout 26％(Xu,1981;Xiao,1981).One of the most important causes of low yield is the defi-ciency in nutrients including zinc.Zinc deficiency usually occurs in calcareous paddy soils withpH>6.5(Zhu and Liu,1981).And the availability of zinc in calcareous paddy soils is lowerthan that in neutral and acid paddy soils.     

Effect of Zinc × Boron Interaction on Plant Growth and Tissue Nutrient Concentration of Corn

ABSTRACT

A pot experiment was conducted in a greenhouse on a calcareous soil (fine, mixed, mesic, Fluventic Haploxerepts) to study the interaction of zinc (Zn) and boron (B) on the growth and nutrient concentration of corn (Zea mays L.). Treatments consisted of a factorial arrangement of seven levels of B (0, 2.5, 5, 10, 20, 40, and 80 mg kg^{? 1}as boric acid), two sources of Zn [zinc sulfate (ZnSO₄ · 7H₂O) and zinc oxide (ZnO)], and three levels of Zn (0, 5, and 10 mg kg^{? 1}) in a completely randomized design with three replications. Plants were grown for 70 d in 1.6 L plastic containers. Applied Zn significantly increased plant height and dry matter yield (DMY) of corn. Source of Zn did not significantly affect growth or nutrient concentration. High levels of B decreased plant height and DMY. There was a significant B × Zn interaction on plant growth and tissue nutrient concentration which were rate dependent. In general, the effect of B × Zn interaction was antagonistic on nutrient concentration and synergistic on growth. It is recommended that the plants be supplied with adequate Zn when corn is grown in high B soils, especially when availability of Zn is low.     

Removal of Cyanide and Zinc–Cyanide Complex by an Ion-Exchange Process

Removal efficiencies of cyanide and a zinc–cyanide complex in solutions were studied by using an ion-exchange process at pH 10.0 and 12.0. An anion-exchange resin, AMBERLITE® IRA-402 Cl, was used to perform packed bed continuous experiments. For the initial 200 mg/l cyanide solution, the packed bed gave a cyanide effluent concentration of 0.2 mg/l at 80 bed volumes for both pH 10.0 and 12.0. Comparatively, in the mixture of 200 mg/l cyanide and 100 mg/l zinc, packed bed volumes were obtained as 80 and 90 at pH 10.0 and 12.0, respectively, to have 0.2 mg/l cyanide effluent concentrations. The packed beds were exhausted at 250 and 400 bed volumes for cyanide and zinc–cyanide complex solutions, respectively. Speciation calculations in Zn(II)/cyanide/OH^? were used to interpret the results. The exchange capacities of the resin were determined as ～1.2 and ～0.9 meq/ml resin for cyanide and zinc–cyanide complex solutions, respectively, and were independent of pH in the studied pH range.     

Distribution of Total and DTPA‐Extractable Zinc,Copper, Manganese,and Iron in Vertisols of India

Abstract

Vertisols of India are developed over isohyets of 600 to 1500 mm, and their chemical cycles are set by drainage, landforms, and particle size, which results in variable pedogenic development within the otherwise homogeneous soils. The purpose of this study was to identify pedogenic processes in the distribution of total and DTPA‐extractable zinc (Zn), copper (Cu), manganese (Mn), and iron (Fe). The soils are developed over basaltic parent material of Cretaceous age. Soil samples were drawn from genetic horizons of the 13 benchmark profiles and analyzed by using HF–HClO₄ acid for total and DTPA extraction. Correlation coefficients were calculated taking all samples together. The total concentration varied from 24 to 102 mg kg^?1 for Zn, 21 to 148 mg kg^?1 for Cu, 387 to 1396 mg kg^?1 for Mn, and 2.36 to 9.50% for Fe. Their variability was proisotropic and haplodized, and their concentrations increased with advancing isohyets. Within the isohyets, hindrance in drainage caused retention of Zn and Cu but loss of Fe. The piedmont soils had more Fe than alluvium soils. The spatial distribution of total contents of Zn, Cu, and Fe was influenced by the pedogenic processes associated with Haplusterts but not with provenance materials. Surface concentrations of the elements by biotic lifting and/or harvest removal were negated by the pedoturbation that further contributed to the irregular distribution of the elements in the profiles. Total Zn and total Cu had positive coefficients of correlations with coarse clay, whereas total Mn and total Fe were positively correlated with fine clay. The DTPA‐extractable forms were functions of isohyets and drainage and showed association with organic carbon content and coarse clay.     

Phosphorus–Zinc Interactions in Two Barley Cultivars Differing in Phosphorus and Zinc Efficiencies

Abstract

Phosphorus (P)–zinc (Zn) interactions in two barley cultivars (Clipper and Sahara) differing in P and Zn efficiencies were investigated in a pot experiment carried out in a growth chamber. A highly calcareous field soil from a semi‐arid region of South Australia was used. Five levels of P addition and three levels of Zn addition were used. Plants were harvested five weeks after emergence. Increase in P supply significantly increased plant shoot biomass and tissue P concentrations in both cultivars, indicating that the soil used is P deficient. Zinc additions with low P additions caused slight decreases in plant biomass. However, Zn addition did increase plant growth when higher levels of P were applied demonstrating the importance of the balance Zn and P supply. Results showed that the genotypic difference between the two cultivars in P uptake efficiency (specific P uptake, SPU) can be altered by Zn–P interactions, and that total Zn uptake by Sahara was higher than Clipper irrespective of P supply. Tissue Zn concentrations decreased significantly with an increase in P supply in both cultivars. Increase in P supply drastically reduced the molar ratio of Zn to P in shoots (MRZP), and addition of Zn compensated for the reduction in MRZP due to P addition. The role of P–Zn interactions in the context of nutritional quality of plant food is also discussed.     

Impact of Postharvest Sprays of Nitrogen,Boron and Zinc on Nutrition,Reproductive Response and Fruit Quality of ‘Schattenmorelle’ Tart Cherries

The aim of the study was to examine effects of fall sprays of nitrogen (N), boron (B) and zinc (Zn) on nutrition, reproductive response, and fruit quality of tart cherry (Prunus cerasus L.). The experiment was conducted during 2008–2010 in Poland on mature ‘Schattenmorelle’ sour cherry trees, planted at a spacing of 4.0 × 1.5 m on a coarse-textured soil with low level of organic matter, and adequate reaction and availabilities of macro- and micronutrients. Tart cherries were sprayed with boric acid-B, ethylenediaminetetraacetic acid (EDTA)-Zn, and urea-N at 40–50 d prior to initiation of leaf fall according to following schema: (i) spray of N at a rate of 23 kg ha^?1; (ii) spray of B and Zn at doses of 1.1 kg ha^?1 and 0.5 kg ha^?1, respectively; and (iii) spray of N, B, and Zn at the same rates as in the above spray combinations. The trees sprayed with water were served as the control. The results showed that postharvest spray treatments had no effect on defoliation, cold damage of flower buds, fruit set, yielding, plant N status, mean fruit weight, and soluble solids concentration in fruit. Postharvest sprays of B and Zn with or without N enhanced status of Zn and B in fall leaves, and B in flowers but had no impact on levels of the above micronutrients in summer leaves. Leaf-absorbed B was withdrawn in the fall, whereas Zn was immobile. It is concluded that postharvest B sprays can be recommended to increase B status in flowers of tart cherry, whereas fall sprays of urea-N and Zn are not able to improve plant nutrition of those nutrients the following season.     

Zinc nutrition and levels of endogenous lndole‐3‐acetic acid in radish shoots

Radish (Raphanus sativus cv. Akamaru‐Hatsukadaikon) was grown for several experiments in a glasshouse with zinc (Zn) supply in the nutrient solution. Lack of Zn resulted in stunted growth and reduced leaf of radish shoots were observed. Two‐dimensional thin layer chromatography (TLC) and gas chromatography‐mass spectrometry (GC‐MS) analysis revealed the presence of endogenous indole‐3‐acetic acid (IAA) in Zn‐deficient radish shoots. An estimate has been made of alkali‐labile (1 and 7N NaOH) IAA in Zn‐deficient radish shoots with the use of gas chromatography (GC). The level of 7N NaOH‐labile IAA (peptidic + ester + free) and IN NaOH‐labile IAA (ester + free) in Zn‐deficient radish shoots was almost the same as that of control radish shoots. These results suggest that Zn nutrition did not affect the level of endogenous IAA in radish shoots.     

Determination of Uranium and Thorium in Soil and Plant Parts around Abandoned Lead–Zinc–Copper Mining Area

This study reports distribution of uranium (U) and thorium (Th) in soil samples and the roots and shoots of some plants grown around an abandoned lead (Pb)–zinc (Zn)–copper (Cu) mining area. The plants Euphorbia macroclada, Verbascum cheiranthifolium Boiss, and Astragalus gummifer were examined. The determinations of U and Th were carried out by inductively coupled plasma‐mass spectrometry (ICP‐MS). Uranium and Th levels of the studied soil samples were found to be in the range of 1.1–70.3 mg kg^?1 and 2.1–62.1 mg kg^?1, respectively. Some results obtained from this study were higher than the mean U and Th concentrations of soils reported around the world. Uranium and thorium concentrations in studied plant roots were in the range of 0.04–16 and 0.08–14.57 mg kg^?1, whereas in plant shoots they were 0.02–2.76 and 0.07–12.3 mg kg^?1, respectively. It was concluded that the shoots of Astragalus and roots of Euphorbia and Verbascum can be used as both a biomonitor for environmental pollution and biogeochemical indicator because of their higher U and Th concentrations.     

Distribution of Forms of Zinc and Their Association with Soil Properties and Uptake in Different Soil Orders in Semi‐arid Soils of Punjab,India

Abstract

Profiles of semi‐arid–zone soils in Punjab, northwest India, were investigated for different forms of zinc (Zn), including total, diethylenetriamine penta‐acetic acid (DTPA)-extractable, soil solution plus exchangeable (Zn), Zn adsorbed onto inorganic sites, Zn bound by organic sites, and Zn adsorbed onto oxide surfaces. Irrespective of the different fractions of Zn present, its content was higher in fine‐textured Alfisols and Inceptisols than in coarse‐textured Entisols. In general, the higher content of Zn was observed in the surface horizon and then decreased in the subsurface horizons. However, none of the forms of Zn exhibited any consistent pattern of distribution. Organic matter and size fractions (clay and silt) had a strong influence on the distribution of different forms of Zn. Based upon the linear coefficient of correlation, the soil solution plus exchangeable Zn, adsorbed onto inorganic sites, and DTPA‐Zn increased with increase in organic carbon but decreased with increase in pH and calcium carbonate content. Total Zn increased with increase in clay and silt content. Among the different forms, Zn bound by organic sites, water soluble plus exchangeable Zn and Zn adsorb onto oxide (amorphous surfaces) were all correlated with DTPA extractable Zn. The uptake of Zn was more in recent floodplain Entisols than very fine textured Alfisols and Inceptisols. Among the different forms soil solution +exchangeable and DTPA‐extractable Zn was positively correlated with total uptake of Zn.     

Phytosequestration of Carbon in Miscanthus × giganteus and Pinus sylvestris L. in Degraded Zinc Smelter and Post-Mining Soils

正Dear Editor,Pinus sylvestris L.is one of the most popular and predominant tree species in Central Europe and Scandinavia.Its cultivation depends on atmospheric conditions,soil fertility,use of fertilizers,and individual characteristics of the trees.Pinus sylvestris L.wood,roots,and needles are used for energy production.Pi-     

Effect of Olive‐Derived Organic Amendments on Lead,Zinc, and Biochemical Parameters of an Artificially Contaminated Soil

Abstract

An incubation experiment was conducted to ascertain the effects of three olive‐derived organic amendments (fresh, compost, and vermicompost olive cake) on the soluble and diethylenetriamine pentaacetic acid (DTPA)–extractable lead (Pb) and zinc (Zn) and on different enzymatic activities in an artificially contaminated calcareous soil. Application of the compost and vermicompost, which increased amounts of humic acids in soil, initially stimulated dehydrogenase, ß‐glucosidase, and urease activities, which tended to decline afterward. In contrast, dehydrogenase and ß‐glucosidase activities were lower after application of the fresh olive cake. Amounts of soluble Pb and Zn increased when fresh olive cake was added to the soil, due to the high content of water‐soluble carbon in this amendment. On the contrary, application of the compost and vermicompost decreased the concentration of soluble Zn and did not change the soluble Pb levels in the soil. The DTPA‐Pb and DTPA‐Zn were scarcely affected by the application of the three olive‐derived amendments.     

Zinc sorption–desorption by sand,silt and clay fractions in calcareous soils of Iran

Zinc sorption–desorption by sand, silt and clay fractions of six representative calcareous soils of Iran were measured. Sand, silt and clay particles were fractionated after dispersion of soils with an ultrasonic probe. Zinc sorption analysis was performed by adding eight rates of Zn from 6 to 120 μmol g^?1. For the desorption experiment, samples retained after the measurement of Zn sorption were resuspended sequentially in 0.01 M NaNO₃ solution and shaken for 24 h. Results indicated that Zn sorption by soil fractions increased in the order clay > silt > sand, and correlated negatively with CaCO₃ content and positively with cation exchange capacity (CEC) and smectite content. Results indicated that for all fractions, the Langmuir equation described the sorption rates fairly well. In contrast to sorption, Zn desorption from soil fractions increased in the order sand > silt > clay, and correlated positively with CaCO₃ content, CEC and smectite content. Results showed that parabolic diffusion and two constant equations adequately described the reaction rates of Zn desorption. In general, for all soils studied, the coarser the particle size, the less Zn sorption and more Zn desorption, and this reflects much higher risk of Zn leaching into groundwater or plant uptake in contaminated soils.     

Zinc‐stress response in some sorghum hybrids and parent cultivars: Significance of pH reduction and recovery from chlorosis

Zinc deficiency was induced in two sorghum hybrids and their parent cultivars by growing them in complete nutrient medium for 30 days and then transferring to minus zinc medium at pH 6.4. The onset of Zn chlorosis and recovery as well as the change in the pH of the nutrient medium under Zn‐stress conditions were recorded. It was found that chlorotic symptoms due to Zn deficiency appeared after 2 days of stress and persisted for a long period in the cultivars, 36‐A and 168, while the hybrid CSH‐7 (36‐A X 168) recovered from chlorosis after 12 days. The hybrid CSH‐8 (36‐A X PD‐3) was chlorotic after 2 days, but recovered after 15 days.

A significant hybrid vigor was observed for Zn‐stress tolerance in the hybrid CSH‐7 and CSH‐8.     

Zinc,copper, and nickel availabilities as determined by soil solution and DTPA extraction of a sludge‐amended soil

Abstract

Extracting sludge‐amended soil with DTPA does not always give a reliable measure of plant‐available heavy metals. The major purpose of this greenhouse pot study was to help explain why. Two anaerobically digested sludges from sewages treated with either Ca(OH)₂or FeCl₃were applied to 3‐kg samples of a Mollic Albaqualf previously limed with Ca(OH)₂rates of 0, 2.5, and 10g/pot that resulted in pHs in the check pots of 5.4, 6.2, or 7.7 after the first harvest. Sludge rates provided 0, 200, 40, 800, and 1600 mg Zn kg^‐1of soil. Two consecutive crops of soybeans (Glycine MaxL.) were grown for 42 d each in the greenhouse. DTPA‐extractable, soil‐solution, and plant concentrations of Cu²⁺, Ni²⁺, and Zn²⁺were measured.

Dry matter yields were depressed due to salt toxicity, while DTPA‐extracted Cu²⁺correlated with plant uptake of Cu²⁺for both sludges. DTPA‐extracted Ni²⁺also correlated with plant Ni²⁺from the Ca(OH)₂‐sludge‐amended soil, although DTPA‐extracted Ni²⁺did not correlate with plant uptake of Ni²⁺from the FeCl₃‐sludge‐amended soil, DTPA‐extracted Zn did not correlate with plant uptake of Zn²⁺from any sludge‐amended soil. Soil‐solution composition correlated with plant uptake of Cu²⁺and Ni²⁺in both sludges; it also correlated with plant uptake of Zn²⁺from FeCl₃‐sludge‐amended soil but not from Ca(OH)₂‐sludge‐amended soil. DTPA extraction probably failed with Ni²⁺and Zn²⁺because of (i) its ineffectiveness at low pH, (ii) the inability of DTPA to buffer each soil extract near pH 7.3, and (iii) increased amounts of soluble chelated micronutrients at higher sludge rates and higher soil pHs. Soil‐solution composition seemed to fail only where micronutrient cations in solution probably were present largely as organic chelates     

Effect of pH on Zinc Sorption–Desorption by Soils

The objective of this study was to examine the effect of soil pH on zinc (Zn) sorption and desorption for four surface soils from the Canterbury Plains region of New Zealand. Zinc sorption by the soils, adjusted to different pH values, was measured from various initial solution Zn concentrations in the presence of 0.01 M calcium nitrate [Ca(NO₃)₂]. Zinc desorption isotherms were derived from the cumulative Zn desorbed (µg g^?1 soil) after each of 10 desorption periods by sequentially suspending the same soil samples in fresh Zn‐free 0.01 M Ca(NO₃)₂. Zinc sorption and desorption varied widely with soil pH. Desorption of both native and added Zn decreased continuously with rising pH and became very low at pH values greater than 6.5. The proportion of sorbed Zn that could be desorbed back into solution decreased substantially as pH increased to more than 5.5. However, there were differences between soils regarding the extent of the hysteresis effect.     

Adsorption of Copper,Zinc, and Cadmium on Goethite,Aluminum‐Substituted Goethite,and a System of Kaolinite–Goethite: Surface Complexation Modeling

Abstract

Goethite, aluminum‐(Al)‐substituted goethite (GA2), and a system of kaolinite–goethite were examined for their ability to adsorb copper (Cu), zinc (Zn), and cadmium (Cd) as a function of pH, in two ionic strengths and two different metal concentrations. Specific surface area was determined by BET‐N₂, whereas the charge development on the solid surface was studied in the pH range ～3.5 to ～10.0 by potentiometric titration under continuous flow of argon.

Constant capacitance (CCM) and the double‐layer model (DLM) were used to fit the titration and adsorption data with the help of the least‐square optimization program FITEQL32. In both models, surface site density was fixed at Ns=2.31 sites nm^?2, whereas for CCM capacitance density was set at C=1.06. Alternatively, bibliographic suggestions for these two parameters were examined.

Aluminum‐substituted goethite exhibited higher specific surface area and adsorbed all three metals in lower pH values than the other solids. Moreover, GA2 exhibited point of zero salt effect (PZSE) higher than goethite, approaching that corresponding to Al₂O₃, possibly due to Al‐substitution, and the system exhibited PZSE values much higher than kaolinite, approaching that corresponding to goethite. The adsorption order for all three solids was Cu>Zn>Cd in any case, thus more Cu is adsorbed at a certain pH than Zn and even more than Cd, whereas the increase of metal concentration shifts the adsorption curve toward higher pH values.

Constant capacitance described the titration data satisfactorily, but by altering the Ns and C values, the fit became worse. Adsorption data are described by CCM, by emphasizing the formation of monodentate surface complex. Bidentate complex, in most of the cases, was of no importance in describing the data despite the evidence of its presence in recent spectroscopic studies for Cu and Cd on goethite. Alteration of Ns and C values worsened the fit in any case, and bidentate complex vanished. The DLM exhibited the worse fit in any case.